A Sb-doped perovskite fluorescent material and color-changing method and application

Abstract

The invention discloses a Sb-doped perovskite fluorescent material and a color-changing method and application, belonging to the technical field of luminescent materials. The invention prepares a water-induced luminescent color-changing material Cs4Bi by a grinding solid phase method. 0.92 Cl7:0.08Sb 3+ The material has a fast water response, good stability, high reversible repeatability and good water-induced luminescence color change phenomenon. After adding water, it will change from yellow luminescence to green luminescence under ultraviolet light. It can be well applied to anti-counterfeiting technology and is suitable for industrial production. In addition, the preparation method of the present invention has cheap and easy-to-obtain raw materials, does not require high-temperature sintering, has no harmful waste, has mild reaction conditions, and does not require further purification of the material.

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent materials, and in particular relates to an Sb-doped perovskite fluorescent material and a color changing method and application thereof. Background Art

[0002] Hydrochromic materials can respond to water by producing photoluminescence changes, which is suitable for anti-counterfeiting technology applications. The slow response and moderate reversibility of most organic hydrochromic materials currently limit their practical applications. As for the new perovskite hydrochromic CsPbBr3 nanocrystals, they are toxic, complex to synthesize, and difficult to mass produce. Other hydrochromic materials also have problems such as expensive raw materials. Summary of the invention

[0003] The main purpose of the present invention is to provide a Sb-doped perovskite fluorescent material and a color changing method and application.

[0004] To achieve the above object, the present invention provides a Sb-doped perovskite fluorescent material, the structural formula of which is: Cs4Bi 0.92 Cl7:0.08Sb 3+ .

[0005] Sb 3+ As the luminescent center ion, the impurity energy level after being doped into Cs4BiCl7 can match the energy level of the Cs4BiCl7 matrix material, playing a leading role in the electron transition, and can undergo transition luminescence under the excitation of ultraviolet wavelengths.

[0006] The preparation method of the Sb-doped perovskite fluorescent material comprises the following steps: BiCl3, Sb2O3 and CsCl are mixed, and concentrated HCl is added thereto for grinding to obtain the Sb-doped perovskite fluorescent material.

[0007] On the one hand, concentrated HCl can inhibit the hydrolysis of BiCl3 and promote the progress of the reaction. On the other hand, concentrated HCl reacts with Sb2O3 to produce SbCl3 precursor, which can generate Cs4Bi 0.92 Cl7:0.08Sb 3+ Fluorescent materials, if there is a lack of concentrated HCl during the preparation process, Cs4Bi cannot be synthesized 0.92 Cl7:0.08Sb 3+ Sb-doped perovskite fluorescent materials with this structure.

[0008] As a further improvement of the present invention, the molar ratio of BiCl3, Sb2O3, and CsCl is 0.92:0.04:4.

[0009] The present invention also claims to protect the color changing method of the Sb-doped perovskite fluorescent material, comprising: under 371nm light irradiation, the Sb-doped perovskite fluorescent material changes from yellow luminescence to green luminescence after adding water, and returns to yellow luminescence after heating and evaporating the water.

[0010] The present invention also requires the application of the Sb-doped perovskite fluorescent material in anti-counterfeiting or light storage.

[0011] Principle of the invention:

[0012] Cs4Bi of the present invention 0.92 Cl7:0.08Sb 3+ Fluorescent materials react with water. Since part of CsCl dissolves in water, the fluorescent material tends to form Cs3Bi 0.92 Cl6:0.08Sb 3+ , after the water evaporates, it can return to the original Cs4Bi 0.92 Cl7:0.08Sb 3 + , because the transformation of the crystal structure causes the change of its luminescence properties.

[0013] Beneficial effects of the present invention: The present invention prepares a zero-dimensional hydroluminescent color-changing material Cs4Bi by a grinding solid phase method. 0.92 Cl7:0.08Sb 3+ The material has a fast water response, good stability, high reversible repeatability and good water-induced luminescence color change phenomenon. After adding water, it will change from yellow luminescence to green luminescence under ultraviolet light. It can be well applied to anti-counterfeiting technology and is suitable for industrial production. In addition, the preparation method of the present invention has cheap and easy-to-obtain raw materials, does not require high-temperature sintering, has no harmful waste, has mild reaction conditions, and does not require further purification of the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 This is the XRD pattern of the Sb-doped perovskite fluorescent material prepared in Example 1 of the present invention.

[0015] Figure 2 This is a comparison chart of the original emission and the emission fluorescence after adding water of the Sb-doped perovskite fluorescent material prepared in Example 1 of the present invention under 371nm excitation.

[0016] Figure 3 This is a luminescence image of the Sb-doped perovskite fluorescent material prepared in Example 1 of the present invention under 371nm excitation emission.

[0017] Figure 4 This is a luminescence image of the Sb-doped perovskite fluorescent material prepared in Example 1 of the present invention after adding water under 371nm excitation emission.

[0018] Figure 5 This is the XRD diagram of the perovskite material prepared in Comparative Example 1 of the present invention.

[0019] Figure 6 This is an XRD diagram of the phase transition of the Sb-doped perovskite fluorescence after adding water prepared in Example 1 of the present invention.

[0020] Figure 7 The luminescence diagrams of the perovskite fluorescence doped with different proportions of Sb prepared in Comparative Examples 2-4 and Example 1 of the present invention under 371nm excitation emission: 0.04Sb is the material prepared in Comparative Example 3, 0.08Sb is the material prepared in Example 1, 0.12Sb is the material prepared in Comparative Example 4, and 0.16Sb is the material prepared in Comparative Example 2. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. In the absence of conflict, the embodiments in this application and the features in the embodiments can be combined with each other. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the art without making creative work are within the scope of protection of the present invention.

[0022] Example 1

[0023] The present invention provides a method for preparing a Sb-doped perovskite fluorescent material, comprising the following steps: mixing 0.92 mmol BiCl3, 0.04 mmol Sb2O3, and 4 mmol CsCl, dropping 0.05 mmol concentrated HCl into the mixture, and grinding the mixture to obtain a Sb-doped perovskite fluorescent material having the structural formula: Cs4Bi 0.92 Cl7:0.08Sb 3+ .

[0024] Depend on Figure 1 It can be seen that the XRD patterns of the synthesized Sb-doped perovskite fluorescent materials are similar to those of Cs4Bi 0.92 Cl7's PDF card PDF#22-0172 has a higher degree of consistency because Bi 3+ and Sb 3+ The ion size is not much different, so it is determined that Cs4Bi 0.92 Cl7:0.08Sb 3+ Successfully synthesized.

[0025] Depend on Figure 2-4 It can be seen that the Cs4Bi 0.92 Cl7:0.08Sb 3+When the fluorescent material is excited by 372nm light, the material changes from yellow light (the luminescence center of yellow light is 550nm) to green light (the luminescence center of green light is 520nm) after adding water. The reaction time is 3-5 seconds, and as the water evaporates, it can return to the original Cs4Bi 0.92 Cl7:0.08Sb 3+ .

[0026] Comparative Example 1

[0027] The present invention provides a method for preparing a perovskite fluorescent material, comprising the following steps: mixing 0.92 mmol BiCl3 and 4 mmol CsCl, dropping 0.05 mmol concentrated HCl into the mixture, and grinding the mixture to obtain a perovskite fluorescent material having the structural formula: Cs4Bi 0.92 Cl7.

[0028] Depend on Figure 5 It can be seen that the XRD of the synthesized perovskite fluorescent material is highly consistent with the PDF card PDF#22-0172 of Cs4BiCl7, indicating that Cs4Bi 0.92 Cl7 was successfully synthesized. However, the prepared Cs4BiCl7 material did not emit light under ultraviolet light.

[0029] Comparative Example 2

[0030] The present invention provides a method for preparing a Sb-doped perovskite fluorescent material, comprising the following steps: mixing 0.84 mmol BiCl3, 0.08 mmol Sb2O3, and 4 mmol CsCl, dropping 0.05 mmol concentrated HCl into the mixture, and grinding the mixture to obtain a Sb-doped perovskite fluorescent material having the structural formula: Cs4Bi 0.84 Cl7:0.16Sb 3+ .

[0031] Comparative Example 3

[0032] The present invention provides a method for preparing a Sb-doped perovskite fluorescent material, comprising the following steps: mixing 0.96 mmol BiCl3, 0.02 mmol Sb2O3, and 4 mmol CsCl, dropping 0.05 mmol concentrated HCl into the mixture, and grinding the mixture to obtain a Sb-doped perovskite fluorescent material having the structural formula: Cs4Bi 0.96 Cl7:0.04Sb 3+ .

[0033] Comparative Example 4

[0034] The present invention provides a method for preparing a Sb-doped perovskite fluorescent material, comprising the following steps: mixing 0.88 mmol BiCl3, 0.06 mmol Sb2O3, and 4 mmol CsCl, dropping 0.05 mmol concentrated HCl into the mixture, and grinding the mixture to obtain a Sb-doped perovskite fluorescent material having the structural formula: Cs4Bi 0.88 Cl7:0.12Sb 3+ .

[0035] The Sb-doped perovskite fluorescent material prepared in Comparative Example 2-4 changes from yellow light to green light when water is added under 371nm light excitation, but the luminescence intensity is lower than that of Example 1. 3+ Too much or too little will result in reduced luminous intensity.

[0036] Comparative Example 5

[0037] The present invention provides a method for preparing a Sb-doped perovskite fluorescent material, comprising the following steps: mixing 0.92 mmol BiCl3, 0.04 mmol Sb2Cl3, and 4 mmol CsCl, grinding the mixture at room temperature, dispersing the mixture in 20 mL chloroform, ultrasonicating the mixture at 300 W ultrasonic power for 20 min, and centrifuging the mixture to obtain a Sb-doped perovskite fluorescent material in the supernatant, wherein the structural formula of the material is: Cs3Bi 0.92 Cl6:0.08Sb 3+ .

[0038] Comparative Example 5: Cs4Bi cannot be synthesized 0.92 Cl7:0.08Sb 3+ Instead, green-emitting Cs3Bi was synthesized 0.92 Cl6:0.08Sb 3+ materials, but without hydrochromic luminescent behavior.

[0039] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A Sb-doped perovskite fluorescent material, characterized in that: Its structural formula is: Cs4Bi 0.92 Cl7:0.08Sb 3+ .

2. The Sb-doped perovskite fluorescent material according to claim 1, characterized in that: The preparation method of the Sb-doped perovskite fluorescent material comprises the following steps: BiCl3, Sb2O3 and CsCl are mixed, and concentrated HCl is added thereto for grinding to obtain the Sb-doped perovskite fluorescent material.

3. The Sb-doped perovskite fluorescent material according to claim 2, characterized in that: The molar ratio of BiCl3, Sb2O3 and CsCl is 0.92:0.04:

4.

4. The color changing method of the Sb-doped perovskite fluorescent material according to any one of claims 1 to 3, characterized in that: include: Under 371nm light irradiation, the Sb-doped perovskite fluorescent material changes from yellow emission to green emission after adding water, and returns to yellow emission after heating and evaporating the water.

5. Use of the Sb-doped perovskite fluorescent material according to any one of claims 1 to 3 in anti-counterfeiting or light storage.

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